PT86893B - PROCESS FOR THE PREPARATION OF A VINYL CHLORIDE POLYMER - Google Patents
PROCESS FOR THE PREPARATION OF A VINYL CHLORIDE POLYMER Download PDFInfo
- Publication number
- PT86893B PT86893B PT86893A PT8689388A PT86893B PT 86893 B PT86893 B PT 86893B PT 86893 A PT86893 A PT 86893A PT 8689388 A PT8689388 A PT 8689388A PT 86893 B PT86893 B PT 86893B
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- Prior art keywords
- vinyl chloride
- polymerization
- oxidant
- process according
- dispersion
- Prior art date
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 56
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000000375 suspending agent Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 235000006708 antioxidants Nutrition 0.000 claims description 53
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- -1 3,5-di — t-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims 1
- 150000002688 maleic acid derivatives Chemical class 0.000 claims 1
- 229920001567 vinyl ester resin Polymers 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 abstract description 7
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- NEIOXSKRYNIBEI-UHFFFAOYSA-N 2-methoxypropoxycarbonyloxy 2-methoxypropyl carbonate Chemical compound COC(C)COC(=O)OOC(=O)OCC(C)OC NEIOXSKRYNIBEI-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- IAWYWVVBKGWUEP-UHFFFAOYSA-N benzyl phenylmethoxycarbonyloxy carbonate Chemical compound C=1C=CC=CC=1COC(=O)OOC(=O)OCC1=CC=CC=C1 IAWYWVVBKGWUEP-UHFFFAOYSA-N 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- CIYGMWIAXRMHQS-UHFFFAOYSA-N ditert-butyl oxalate Chemical compound CC(C)(C)OC(=O)C(=O)OC(C)(C)C CIYGMWIAXRMHQS-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- DHRQKFYLKJURNK-UHFFFAOYSA-N dodecoxycarbonyloxy dodecyl carbonate Chemical compound CCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCC DHRQKFYLKJURNK-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- NTEMPNAZVJDCJF-UHFFFAOYSA-N hexadecoxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOOC(=O)OCCCCCCCCCCCCCCCC NTEMPNAZVJDCJF-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229960002900 methylcellulose Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- PFADVMKRWMHNTC-UHFFFAOYSA-N tert-butyl (2-methylpropan-2-yl)oxycarbonyloxy carbonate Chemical compound CC(C)(C)OC(=O)OOC(=O)OC(C)(C)C PFADVMKRWMHNTC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Antecedentes da invençãoBackground of the invention
1. Âmbito da invenção1. Scope of the invention
A presente invenção refere-se a um processo para a preparação de um polímero de cloreto de vinilo mediante polimerização em suspensão em um meio aquoso.The present invention relates to a process for the preparation of a vinyl chloride polymer by polymerization in suspension in an aqueous medium.
2. Descrição da técnica anterior2. Description of the prior art
Convencionalmente, é costume adicionar um antioxidante a um sistema de polimerização quando se prepara um polímero de cloreto de vinilo, o qual se adiciona com o objectivo de:Conventionally, it is customary to add an antioxidant to a polymerization system when preparing a vinyl chloride polymer, which is added in order to:
1) retardar ou terminar a reacção de polimerização,1) delay or terminate the polymerization reaction,
2) dispersar homogeneamente o antioxidante num produto de resina de cloreto de vinilo resultante para evitar a deterioração de resina de cloreto de vinilo, etc. Em qualquer caso, o antioxidante necessita de ser disperso homogeneamente no sistema de polimerização em suspensão para tornar máximo o efeito da adição do antioxidante.2) homogeneously disperse the antioxidant in a resulting vinyl chloride resin product to prevent deterioration of vinyl chloride resin, etc. In any case, the antioxidant needs to be dispersed homogeneously in the suspension polymerization system to maximize the effect of adding the antioxidant.
antioxidante inclui, convencionalmente, antioxidantes de fenol, de amina, de enxofre, de fósforo, etc., que todavia são, em geral, pulverulentos, dificultando o seu carregamento automático numa quantidade pré-determinada. Particularmente, durante a polimerização é especialmente difícil pressionar uma quantidade desejada do antioxidante pulverulento no sistema que se conserva num estado pressurizado.An antioxidant conventionally includes phenol, amine, sulfur, phosphorus, etc., which are, however, generally powdery, making it difficult to automatically load them in a predetermined amount. In particular, during polymerization it is especially difficult to press a desired amount of the powdery antioxidant into the system which is kept in a pressurized state.
Por esta razão, normalmente dissolve-se o antioxidante num dissolvente orgânico adequado e adiciona-se sob a forma de solução.For this reason, the antioxidant is usually dissolved in a suitable organic solvent and added in the form of a solution.
-2Este método torna possível carregar automaticamente o anti-oxidante, mas tem tido problemas tais como: ser necessário recuperar o dissolvente, o dissolvente permanecer na resina de cloreto de vinílo resultante provocando um empobrecimento da sua qualidade, misturar o dissolvente nos monómeros a recuperar que não reagiram, e o aumento do COD na água residual no caso da polimerização em suspensão se efectuar num meio aquoso.-2This method makes it possible to automatically load the anti-oxidant, but it has had problems such as: it is necessary to recover the solvent, the solvent remains in the resulting vinyl chloride resin causing an impoverishment of its quality, mixing the solvent in the monomers to recover that they did not react, and the increase in COD in the residual water in the event of suspension polymerization is carried out in an aqueous medium.
Agora, propôs-se recentemente um processo em que se dispersa um anti-oxidante pulverulento em água utilizando um agente emulsionante isolado ou utilizando o agente emulsionante em combinação com um agente de suspensão, para o levar a um estado de emulsão, a qual se adiciona então ao sistema de polimerização (Japanese Unexamined Patent Publications NÔ. 149608/1985 e NQ. 186547/1985) .Now, a process has recently been proposed in which a powdery anti-oxidant is dispersed in water using an isolated emulsifying agent or using the emulsifying agent in combination with a suspending agent, to bring it into an emulsion state, which is added then to the polymerization system (Japanese Unexamined Patent Publications NÔ. 149608/1985 and NQ. 186547/1985).
Contudo, o processo anterior, em que se adiciona o anti-oxidante scb a forma de uma emulsão utilizando um agente emulsionante pode diminuir a estabilidade térmica e a estabilidade de armazenagem da resina de cloreto de vinílo resultante per causa da inclusão do agente emulsionante. Tem também problemas tais como, quando adicionado para terminar a polimerização, a reacção tende a terminar com efeito insuficiente, e, quando adicionado após completada a polimerização, pode acontecer que as características de absorção do plastificante da resina de cloreto de vinílo empobreçam depois da resina ser submetida ao tratamento pelo calor.However, the previous process, in which the anti-oxidant is added in the form of an emulsion using an emulsifying agent can decrease the thermal stability and storage stability of the resulting vinyl chloride resin because of the inclusion of the emulsifying agent. It also has problems such as, when added to finish the polymerization, the reaction tends to end with insufficient effect, and when added after the polymerization is complete, it may happen that the absorption characteristics of the vinyl chloride resin plasticizer deplete after the resin. undergo heat treatment.
Sumário de invençãoSummary of invention
Agora, um objectivo da presente invenção consiste em proporcionar um processo para a preparação de um polímero de cloreto de vinílo, que torna possível o carregamento automático do anti-oxidante sem utilização de qualquer dissolvente nem qualquer agente emulsionante e que consiga suficientemente o efeito pretendido de adicionar o anti-oxidante para se obter uma resina de cloreto de vinílo de alta qualidade.Now, an object of the present invention is to provide a process for the preparation of a vinyl chloride polymer, which makes it possible to automatically load the anti-oxidant without using any solvent or any emulsifying agent and which sufficiently achieves the desired effect of add the antioxidant to obtain a high quality vinyl chloride resin.
Esta invenção proporciona um processo para a preparação de um polímero de cloreto de vinílo mediante polimerização de cloreto de vinílo ou uma mistura de menómeros de vinílo possuindoThis invention provides a process for the preparation of a vinyl chloride polymer by polymerizing vinyl chloride or a mixture of vinyl menomers having
-3L·^ cloreto de vinílo, por meio de uma polimerização em suspensão num meio aquoso, em que se adiciona ao sistema de polimerização anterior, uma dispersão anti-oxidante que inclui um anti-oxidante, um agente de suspensão e água.Vinyl chloride, by means of a suspension polymerization in an aqueous medium, in which an anti-oxidant dispersion is added to the previous polymerization system which includes an anti-oxidant, a suspending agent and water.
Esta invenção torna possível o carregamento automático do anti-oxidante ao sistema de polimerização. 0 polímero de cloreto de vinílo resultante pode ser de elevada gualidade, por ex., de elevada estabilidade na armazenagem, de elevada estabilidade térmica e com elevadas características de absorção do plastificante.This invention makes it possible to automatically load the anti-oxidant into the polymerization system. The resulting vinyl chloride polymer can be of high quality, for example, of high stability in storage, of high thermal stability and with high absorption characteristics of the plasticizer.
Também, pode baixar-se o COD na água residual, trazendo uma grande vantagem ao saneamento ambiental.Also, the COD can be lowered in the waste water, bringing a great advantage to environmental sanitation.
Descrição detalhada da invenção anti-oxidante utilizado nesta invenção pode incluir, por exemplo, antioxidantes de fenol, de amina, de enxofre, de fósforo etc., e são particularmente preferidos os que têm um ponto de fusão o o superior a 30“ C e inferior a 100 C.Detailed description of the anti-oxidant invention used in this invention may include, for example, phenol, amine, sulfur, phosphorus, etc. antioxidants, and those having a melting point greater than 30 “C and below are particularly preferred. at 100 C.
Exemplos do antioxidante com tal ponto de fusão incluem p-metoxifenol, t-butil-hidroxiamisol (BHA), n-octadecil-3-(41 -hidroxi-31,51-di-t-butilfenil) - propionato, 3,5-di-t-butil-4-hidroxitolueno (BHT), glicol-bis- 3-(3-t-butil-5-metil-4-hidroxifenil)-propionato7de trietileno , 1,6-hexanodiol-bisL 3-(3,5-di-t-butil-4-hidroxifenil)-propionato/ , 2,4-bis-(n-octiltio )-6-(4-hidroxi-3,5-di-t-butil-anilino)-1,3,5-triazina, 2,2-tiodietileno-bis-Z~ 3—(3,5-di-t-butil-4-hidroxifenil)-propionatoJZ , 2,2-tiobis-(4-metil-6-t-butilfenol), etc., mas estes exemplos não constituem um limite à presente invenção.Examples of the antioxidant with such a melting point include p-methoxyphenol, t-butylhydroxyamisol (BHA), n-octadecyl-3- (4 1 -hydroxy-3 1 , 5 1 -di-t-butylphenyl) - propionate, 3 , 5-di-t-butyl-4-hydroxytoluene (BHT), glycol-bis- 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -triethylene, 1,6-hexanediol-bisL 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate /, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl-anilino) -1,3,5-triazine, 2,2-thiodiethylene-bis-Z ~ 3— (3,5-di-t-butyl-4-hydroxyphenyl) -propionateJZ, 2,2-thiobis- (4-methyl- 6-t-butylphenol), etc., but these examples do not limit the present invention.
Estes anti-oxidantes podem estar isolados ou podem estar em combinação de dois ou mais. Entre os exemplos de anti-oxidantes anteriores, preferem-se, particularmente, os que incluem trietileno-glicol-bis /, 3-(3-t-butil-5-metil-4-hidroxi-fenil)-propionato_7 , n-octadecil-3-(41-hidroxi-3'-51-di-t-butilfenil)-propionato , t-butil-hidroxianisol , 3,5-di-t-butil-4-hidroxitolueno e 1,6-hexanodiol-bis [_ 3- ( 3,5-di-t-butil-4-hidroxif enil) -propionat</.These anti-oxidants can be isolated or can be in combination of two or more. Among the foregoing examples of anti-oxidants, particularly those which include triethylene glycol-bis /, 3- (3-t-butyl-5-methyl-4-hydroxy-phenyl) -propionate_7, n-octadecyl are particularly preferred -3- (4 1 -hydroxy-3'-5 1 -di-t-butylphenyl) -propionate, t-butyl-hydroxyanisol, 3,5-di-t-butyl-4-hydroxytoluene and 1,6-hexanediol- bis [_ 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionat </.
No processo da presente invenção, o agente de suspensãoIn the process of the present invention, the suspending agent
-4utilizado para a preparação da dispersão anti-oxidante pode incluir, por exemplo, álcool polivinílico, metil-celulose, hidroxi-propil-metil-celulose,hidroxietil-celulose, carboximetil-celulose e similares.-4 used for the preparation of the anti-oxidant dispersion may include, for example, polyvinyl alcohol, methyl cellulose, hydroxy-propyl-methyl-cellulose, hydroxyethyl-cellulose, carboxymethyl-cellulose and the like.
Preferem-se particularmente álcoois polivinílicos solúveis em água com um grau de saponificação de 60 a 98% em moles e um grau de polimerização de 600 a 3000.Particularly preferred are water-soluble polyvinyl alcohols with a degree of saponification of 60 to 98 mole% and a degree of polymerization of 600 to 3000.
Isto porque os que têm um grau de saponificação inferior a 60% em moles podem dissolver-se em água com dificuldade e os álcoois polivinílicos perfeitamente saponifiçados possuindo um grau de saponificação superior a 98% em moles tendem a geleficar durante a armazenagem. Podem também utilizar-se em combinação óxido de polietileno, poliacrilato de sódio, ácido algínico, etc. A dispersão anti-oxidante utilizada na presente invenção pode preparar-se, por exemplo, alimentando com água um tanque de dissolução equipado com uma camisa para aquecimento ou arrefecimento e um agitador, adicionando o agente de suspensão e o anti-oxidante pulverulento, e dispersando-os com agitação. Neste momento,é preferível, após a dispersão do anti-oxidante, aumentar a temperatura para uma temperatura mais elevada que o ponto de fusão do anti-oxidante por aquecimento com a camisa , seguido de arrefecimento quando a dispersão estiver suficientemente homogénea. Em virtude desta operação de aquecimento, pode obter-se a dispersão anti-oxidante como uma dispersão aquosa na qual o anti-oxidante se dispersou homogeneamente.This is because those with a degree of saponification of less than 60% by moles can dissolve in water with difficulty and perfectly saponified polyvinyl alcohols having a degree of saponification greater than 98% by moles tend to gel during storage. Polyethylene oxide, sodium polyacrylate, alginic acid, etc. can also be used in combination. The anti-oxidant dispersion used in the present invention can be prepared, for example, by feeding water to a dissolution tank equipped with a heating or cooling jacket and a stirrer, adding the suspending agent and powdery anti-oxidant, and dispersing them with agitation. At this point, it is preferable, after dispersing the antioxidant, to raise the temperature to a temperature higher than the melting point of the antioxidant by heating with the jacket, followed by cooling when the dispersion is sufficiently homogeneous. As a result of this heating operation, the anti-oxidant dispersion can be obtained as an aqueous dispersion in which the anti-oxidant has homogeneously dispersed.
Não há limite particular para os meios de dispersão utilizados na preparação da dispersão anterior, e a palheta de agitação pode ter uma forma geral tal como uma pá, uma hélice, uma turbina, do tipo Brumagin, do tipo Pfaudler, etc. Se necessário, é também possível utilizar um homogeneizador em combinação, ou pode utilizar-se uma bomba de pressão elevada, um moinho de coloides, a ejecção de pressão elevada através de um bocal ou orifício, ondas ultrassónicas, etc.There is no particular limit on the dispersion media used in the preparation of the previous dispersion, and the stirring vane can have a general shape such as a paddle, propeller, turbine, Brumagin type, Pfaudler type, etc. If necessary, it is also possible to use a homogenizer in combination, or a high pressure pump, a colloid mill, high pressure ejection through a nozzle or orifice, ultrasonic waves, etc. can be used.
As partículas do anti-oxidante disperso na dispersão podem, de preferência, ter um tamanho de partícula de 20 ÂJm ouThe particles of the anti-oxidant dispersed in the dispersion may preferably have a particle size of 20 µm or
-5inferior do ponto de vista de estabilidade de armazenagem e podem estar numa concentração de cerca de 5 a 50% em peso.-5 lower from the point of view of storage stability and can be in a concentration of about 5 to 50% by weight.
Não há também qualquer limite particular para a concentração do agente de suspensão, que pode ser adequadamente seleccionado tendo em conta a estabilidade na armazenagem e a facilidade de ser alimentado por uma bomba (por outras palavras, a viscosidade após formada a dispersão), mas usualmente pode preferir-se que esteja compreendida entre 1 e 30% aproximadamente.There is also no particular limit on the concentration of the suspending agent, which can be appropriately selected taking into account the stability in storage and the ease of being fed by a pump (in other words, the viscosity after the dispersion is formed), but usually it may be preferred to be between 1 and 30% approximately.
Não existe limite particular para a água utilizada na preparação da dispersão, mas prefere-se utilizar água destilada ou desionizada.There is no particular limit for the water used in the preparation of the dispersion, but it is preferred to use distilled or deionized water.
Pode adicionar-se a dispersão anti-oxidante anterior em qualquer altura, isto é, antes de se iniciar a polimerização, durante a polimerização ou após completar a polimerização, dependendo objectivo da adição.The previous anti-oxidant dispersion can be added at any time, that is, before starting the polymerization, during the polymerization or after completing the polymerization, depending on the purpose of the addition.
Usualmente,pode adicionar-se a dispersão anti-oxidante ao sistema de polimerização antes do início da polimerização para controlar a polimerização e assim reduzir os olhos de peixe nos produtos resultantes, no fim da polimerização para terminar a polimerização e depois da polimerização estar completa para evitar a degradação dos produtos resultantes. Pode adicionar-se a dispersão anti-oxidante uma ou mais vezes para conseguir um ou mais dos objectivos anteriores.Usually, the anti-oxidant dispersion can be added to the polymerization system before the polymerization starts to control the polymerization and thus reduce fish eyes in the resulting products, at the end of the polymerization to finish the polymerization and after the polymerization is complete to avoid degradation of the resulting products. The antioxidant dispersion can be added one or more times to achieve one or more of the above objectives.
Para facilidade da operação, deve, de preferência, alimentar-se com uma bomba. Pode adicionar-se a dispersão anti-oxidante, de preferência, numa quantidade (em termos do anti-oxidante) compreendida entre 0,001 e 1,0% (em peso) baseada na quantidade de monómeros a carregar no sistema. Quantidades inferiores a 0,001% tornam impossível evitar que a resina de cloreto de vinilo seja deteriorada e quantidades superiores a 1,0% podem não trazer expectativas de um aperfeiçoamento maior do efeito anti-oxidante, resultando não só numa desvantagem económica mas também num aumento do COD na água residual.For ease of operation, you should preferably use a pump. The anti-oxidant dispersion can preferably be added in an amount (in terms of the anti-oxidant) of between 0.001 and 1.0% (by weight) based on the amount of monomers to be loaded into the system. Quantities of less than 0.001% make it impossible to prevent vinyl chloride resin from deteriorating and quantities of more than 1.0% may not bring expectations of further improvement of the anti-oxidant effect, resulting not only in an economic disadvantage but also in an increase in the COD in wastewater.
Pode aplicar-se o processo desta invenção na polimerizaçãoThe process of this invention can be applied to polymerization
-6c í-6c í
em suspensão aquosa de qualquer monómero de cloreto de vinilo ou misturas de monómeros de vinilo contendo monómero de cloreto de vinilo já conhecidas.in aqueous suspension of any vinyl chloride monomer or mixtures of vinyl monomers containing vinyl chloride monomer already known.
Os monómeros de vinilo diferentes de cloreto de vinilo podem incluir, por exemplo, Ot-olefinas tal como etileno, propileno, 1-buteno, 1-penteno, 1-hexeno, 1-hepteno, 1-octeno, 1-noneno, 1-deceno, 1-undeceno, 1-dodeceno, 1-trideceno e 1-tetradeceno,ácido acrílico e os respectivos ésteres, ácido metacrílico e respectivos ésteres, ácido maleico e respectivos ésteres, compostos de vinilo tais como acetato de vinilo, propionato de vinilo e éteres alquil-vinílicos e uma mistura destes.Vinyl monomers other than vinyl chloride may include, for example, Otolefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, 1-undecene, 1-dodecene, 1-tridecene and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl compounds such as vinyl acetate, vinyl propionate and alkyl vinyl ethers and a mixture of these.
Na polimerização em suspensão aquosa, utilizam-se geralmente 80 a 300 partes em peso de água baseada em 100 partes em peso dos monómeros e efectua-se a polimerização usualmente a uma temperatura compreendida entre 35° e 70° C.In aqueous suspension polymerization, 80 to 300 parts by weight of water based on 100 parts by weight of monomers are generally used and the polymerization is usually carried out at a temperature between 35 ° and 70 ° C.
Os iniciadores de polimerização utilizáveis podem incluir, por exemplo, peroxidi-carbonatos tais como peroxidi-carbonato de di-isopropilo, peroxi-di-carbonato de di-octilo, peroxi-di-carbonato de dilaurilo, peroxi-di-carbonato de dicetilo, peroxi-di-carbonato de di-terc-butilo, peroxidicarbonato de di (2-etoxi-etilo), peroxidicarbonato de di (2-metoxi-propilo), peroxidicarbonato de dibenzilo, peroxidicarbonato de di-ciclo-hexilo e peroxidicarbonato de di-terc-butilciclohexilo; compostos azo tais como 2,2' — -azobis-2,4-dimetilvaleronitrilo e 2,21-azobis-4-metoxi-2,4-dimetilvaleronitrilo; peróxidos tais como peroxineodecanato de terc-butilo, peroxipivarato de terc.-butilo , peroxipivarato de <Sc-cumilo, peroxipivarato de amilo, oxalato de di-terc.-butilo,peróxi de isobutirilo, peroxineodecanato de ter-octilo e peroxineodecanato de -cumilo.Useful polymerization initiators may include, for example, peroxydicarbonates such as diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, dilauryl peroxydicarbonate, dicetyl peroxycarbonate, di-tert-butyl peroxydicarbonate, di (2-ethoxy-ethyl) peroxydicarbonate, di (2-methoxy-propyl) peroxydicarbonate, dibenzyl peroxydicarbonate, di-cyclohexyl peroxydicarbonate and di-cyclohexyl peroxydicarbonate tert-butylcyclohexyl; azo compounds such as 2,2'-azobis-2,4-dimethylvaleronitrile and 2,2 1 -azobis-4-methoxy-2,4-dimethylvaleronitrile; peroxides such as tert-butyl peroxyenedecanate, tert-butyl peroxypivarate, <Sc-cumyl peroxypivarate, amyl peroxypivarate, di-tert-butyl oxalate, isobutyryl peroxide, tert-octyl peroxyethodate and peroxyethylumate peroxyethylate. .
Estes compostos podem ser usados para uniformizar a velocidade da reacção de polimerização. Os dispersantes urilizados na polimerização em suspensão aquosa podem incluir, por exemplo, álcool polivinílico, derivados de celulose, um copolímero de anidrido maleico/estireno, um copolímero de anidrido maleico/éter de metil vinílico, gelatina, etc. Eventualmente, podem adicionar-Ί-These compounds can be used to uniform the rate of the polymerization reaction. Dispersants used in aqueous suspension polymerization can include, for example, polyvinyl alcohol, cellulose derivatives, a maleic anhydride / styrene copolymer, a maleic anhydride / methyl vinyl ether copolymer, gelatin, etc. Eventually, they can add-Ί-
-se ainda reguladores de polimerização apropriados, agentes de transferência de cadeia, aperfeiçoadores da gelatinização,agentes anti-estáticos, ajustadores de pH, etc.appropriate polymerization regulators, chain transfer agents, gelatinization enhancers, antistatic agents, pH adjusters, etc.
ExemplosExamples
Esta invenção será descrita a seguir com maior detalhe por meio de exemplos.This invention will be described in more detail below by way of examples.
Exemplo 1 (1.) Preparação de uma dispersão anti-oxidante aquosa:Example 1 (1.) Preparation of an aqueous antioxidant dispersion:
Numa proveta com um volume interno de 300 cm3, carregaram-se 210 g de água desionizada, 15 g de álcool polivinílico com um grau de saponificação de 79,5% e um grau de polimerização médio de 2,550 e 25 g trietileno-glicol-bis/. 3-(3-t-butil-5-metil-4-hidroxifenil)-propionato7 (p.f: 80° C) e aqueceu-se a 82° C com agitação, seguido do arrefecimento ao mesmo tempo que são homogeneamente dispersos para se obter uma dispersão anti-oxidante aquosa homogénea.In a beaker with an internal volume of 300 cm 3 , 210 g of deionized water, 15 g of polyvinyl alcohol with a degree of saponification of 79.5% and an average degree of polymerization of 2.550 and 25 g of triethylene glycol- were loaded. bis/. 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate7 (mp: 80 ° C) and heated to 82 ° C with stirring, followed by cooling while being homogeneously dispersed to obtain a homogeneous aqueous anti-oxidant dispersion.
(2.) Preparação de um polímero de cloreto de vinilo por polimerização em suspensão:(2.) Preparation of a vinyl chloride polymer by suspension polymerization:
Num vaso de polimerização de aço inoxidável, com um volume interno de 100 litros, carregaram-se 60 Kg de água desionizada, 25 g de álcool polivinílico parcialmente saponificado e 15 g de peroxidicarbonato de di-2-etiHhexilo. Depois de o conteúdo do vaso ter sido submetido a uma pressão de 40 mmHg carregaram-se 30 Kg de monómero de cloreto de vinilo e aqueceu-se a 57° C com agitação, para se efectuar a polimerização enquanto se mantinha a mesma temperatura.In a stainless steel polymerization vessel, with an internal volume of 100 liters, 60 kg of deionized water, 25 g of partially saponified polyvinyl alcohol and 15 g of di-2-ethylhexyl peroxydicarbonate were loaded. After the contents of the vessel were subjected to a pressure of 40 mmHg, 30 kg of vinyl chloride monomer was loaded and heated to 57 ° C with stirring, to carry out the polymerization while maintaining the same temperature.
Nessa altura a pressão no interior do vaso atingiu 6,5 Kg/ /cm2G e injectou-se no vaso, por meio de uma bomba, 150 g da dispersão anti-oxidante aquosa preparada em 1).At that time, the pressure inside the vessel reached 6.5 Kg / / cm 2 G and 150 g of the aqueous anti-oxidant dispersion prepared in 1) was injected into the vessel.
Depois disso, enquanto se recuperara os monómeros que não reagiram, aumentou-se a temperatura no interior do vaso que se man-8-After that, while the unreacted monomers were recovered, the temperature inside the vessel that remained
teve durante 30 minutos a 80° C. Em seguida arrefeceu-se. Desidratou-se e secou-se a pasta de polímero resultante.had for 30 minutes at 80 ° C. Then cooled. The resulting polymer slurry was dehydrated and dried.
Exemplo 2 (1) Preparação da dispersão aquosa de anti-oxidante:Example 2 (1) Preparation of the aqueous dispersion of antioxidant:
Repetiu-se o exemplo 1— (1) para preparar uma dispersão aquosa, excepto pelo facto de se utilizar 10 g de álcool polivinílico e 75 g de trietileno-glicol-bis £3-(3-t-butil-5-metil-4-hidroxifenil)-propionato_7 .Example 1— (1) was repeated to prepare an aqueous dispersion, except that 10 g of polyvinyl alcohol and 75 g of triethylene glycol-bis £ 3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) -propionate_7.
(2) Preparação de polímero de cloreto de vinilo:(2) Preparation of vinyl chloride polymer:
Repetiu-se o exemplo 1—(2) para preparar um polímero de cloreto fie poli vinilo t excepto no facto de se utilizar como dispersão aquosa 50 g da dispersão preparada anteriormente (1).Example 1— (2) was repeated to prepare a polyvinyl chloride polymer t except that 50 g of the previously prepared dispersion (1) is used as an aqueous dispersion.
Exemplo 3 (1) Preparação da dispersão aquosa de anti-oxidante:Example 3 (1) Preparation of the aqueous dispersion of anti-oxidant:
Repetiu-se o exemplo 1~(1) para preparar uma dispersão aquosa, excepto no facto de se utilizar 35 g de álcool polivinílico com um grau de saponificação de 72,5% e um grau de polimerização médio de 780 em vez de 15 g de álcool polivinílico com um grau de saponificação de 79,5% e um grau de polimerização médio de 2.550.Example 1 ~ (1) was repeated to prepare an aqueous dispersion, except that 35 g of polyvinyl alcohol with a degree of saponification of 72.5% and an average degree of polymerization of 780 is used instead of 15 g of polyvinyl alcohol with a saponification degree of 79.5% and an average degree of polymerization of 2,550.
(2) Preparação do polímero de cloreto de vinilo:(2) Preparation of the vinyl chloride polymer:
Repetiu-se o exemplo l-(2) para preparar um polímero de cloreto de vinilo, excepto no facto de se utilizar como dispersão aquosa 162 g da dispersão preparada anteriormente (1).Example 1- (2) was repeated to prepare a vinyl chloride polymer, except that 162 g of the previously prepared dispersion (1) is used as an aqueous dispersion.
Exemplo de comparação 1 (1) Preparação da solução anti-oxidante:Comparison example 1 (1) Preparation of the antioxidant solution:
Dissolveram-se 15 g de trietileno-glicol-bis/. 3-(3“t-butil-5-metil-9-15 g of triethylene glycol-bis / were dissolved. 3- (3 "t-butyl-5-methyl-9-
-4-hidroxifenil-propionato7 em 100 g de metanol (2) Preparação de polímero de cloreto de vinilo:-4-hydroxyphenyl-propionate7 in 100 g of methanol (2) Preparation of vinyl chloride polymer:
Repetiu-se o exemplo l-(2) para preparar um polímero de cloreto de vinilo, excepto no facto de se utilizar a solução de metanol anterior em vez da dispersão aquosa.Example 1- (2) was repeated to prepare a vinyl chloride polymer, except that the above methanol solution was used instead of the aqueous dispersion.
Exemplo de comparação 2 (1) Preparação da dispersão aquosa anti-oxidante:Comparison example 2 (1) Preparation of the aqueous antioxidant dispersion:
Num moinho de bolas,carregaram-se 40 partes (em peso) de trietileno-glicol-bis /~3-(3-t-butil-5-metil-4-hidroxifenil)-propionato/, partes de água desionizada e 3 partes de monolaurato de sorbitano e triturou-se para preparar uma dispersão aquosa homogénea.In a ball mill, 40 parts (by weight) of triethylene glycol-bis / ~ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate were loaded, parts of deionized water and 3 parts of sorbitan monolaurate and ground to prepare a homogeneous aqueous dispersion.
(2) Preparação de polímero de cloreto de vinilo:(2) Preparation of vinyl chloride polymer:
Repetiu-se o exemplo 1—(2) para preparar um polímero de cloreto de vinilo, excepto no facto de se utilizar como dispersão aquosa 37,5 g da dispersão preparada anteriormente (1).Example 1— (2) was repeated to prepare a vinyl chloride polymer, except that 37.5 g of the previously prepared dispersion (1) was used as an aqueous dispersion.
Mediu-se o tamanho das partículas dispersas, a estabilidade na armazenagem e a viscosidade das dispersões anti-oxidantes preparadas nos exemplos e nos exemplos de comparação anteriores. Mediram-se as características de absorção do plastificante e a propriedade de cor inicial dos polímeros de cloreto de vinilo resultantes.The size of the dispersed particles, the storage stability and the viscosity of the anti-oxidant dispersions prepared in the previous examples and comparison examples were measured. The plasticizer absorption characteristics and the initial color property of the resulting vinyl chloride polymers were measured.
Também se mediu o COD na água residual após a polimerização. Apresentam-se os resultados na tabela 1. Calculou-se a estabilidade na armazenagem das dispersões anti-oxidantes e a propriedade de ausência de cor inicial dos polímeros de cloreto de vinilo, com base nos padrões apresentados a seguir. No que se refere às características de absorção do piastificante, deixam-se os polímeros de cloreto de vinilo imersos numa quantidade prescrita de um plastificante. Em seguida, separou-se o plastificante não recuperado por meio de um separador por centrifugação e depois, para fazer o cálculo, determinou-seCOD was also measured in the waste water after polymerization. The results are shown in table 1. The storage stability of the anti-oxidant dispersions and the initial colorless property of the vinyl chloride polymers were calculated, based on the standards presented below. As regards the absorption characteristics of the piastifying agent, the vinyl chloride polymers are left immersed in a prescribed amount of a plasticizer. Then, the non-recovered plasticizer was separated by means of a separator by centrifugation and then, to make the calculation, it was determined
a absorção do plastificante a partir ao aumento de peso dos polímeros de cloreto de vinilo.the absorption of the plasticizer from the increase in weight of the vinyl chloride polymers.
- Estabilidade na armazenagem das dispersões anti-oxidante:- Storage stability of anti-oxidant dispersions:
A: Não se verificou nenhum endurecimento mesmo após 24 horas de repouso.A: There was no hardening even after 24 hours of rest.
B: Ocorre endurecimento após 6 horas ou mais de repouso.B: Hardening occurs after 6 hours or more of rest.
C: Ocorre endurecimento ao fim de uma hora.C: Hardening occurs after one hour.
- Propriedade de cor inicial dos polímeros de cloreto de vinilo:- Initial color property of vinyl chloride polymers:
Fez-se a avaliação em comparação com um polímero de cloreto de vinilo preparado da mesma forma que no exemplo l-(2) excepto no facto de não se introduzir a dispersão aquosa do anti-oxidante.The evaluation was carried out in comparison with a vinyl chloride polymer prepared in the same way as in example 1- (2) except that the aqueous dispersion of the antioxidant is not introduced.
A : SuperiorA: Superior
B : Substancialmente igualB: Substantially the same
C : PobreC: Poor
II
TABELAITABLE
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051641A JPH0788401B2 (en) | 1987-03-06 | 1987-03-06 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PT86893A PT86893A (en) | 1988-04-01 |
| PT86893B true PT86893B (en) | 1992-05-29 |
Family
ID=12892473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PT86893A PT86893B (en) | 1987-03-06 | 1988-03-03 | PROCESS FOR THE PREPARATION OF A VINYL CHLORIDE POLYMER |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5011897A (en) |
| EP (1) | EP0281210B1 (en) |
| JP (1) | JPH0788401B2 (en) |
| MX (1) | MX167103B (en) |
| NO (1) | NO168830C (en) |
| PT (1) | PT86893B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696616B2 (en) * | 1987-03-19 | 1994-11-30 | チッソ株式会社 | Method for producing vinyl chloride polymer |
| JPH0676446B2 (en) * | 1987-10-19 | 1994-09-28 | チッソ株式会社 | Method for producing vinyl chloride polymer |
| JPH0347807A (en) * | 1989-04-14 | 1991-02-28 | Shin Etsu Chem Co Ltd | Method for producing matte vinyl chloride polymer |
| US5214087A (en) * | 1990-03-26 | 1993-05-25 | The B. F. Goodrich Company | Vinyl halide polymer: ethylene-vinyl alcohol blends containing phenolic antioxidant |
| US5767212A (en) * | 1992-06-30 | 1998-06-16 | Toray Industries, Inc. | Method of producing sulfur containing color-free transparent (metha) acrylate polymer having high visible light transmittance |
| CA2110209A1 (en) * | 1992-11-30 | 1994-05-31 | Tadashi Amano | Process for preparing vinyl chloride polymers |
| JP2000290308A (en) | 1999-04-09 | 2000-10-17 | Shin Etsu Chem Co Ltd | Method for producing vinyl chloride polymer |
| JP3802999B2 (en) | 1999-08-09 | 2006-08-02 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| DE10159344A1 (en) | 2001-12-04 | 2003-06-12 | Crompton Vinyl Additives Gmbh | Prestabilization of halogen-containing polymers |
| DK1485441T4 (en) † | 2002-03-21 | 2009-11-23 | Basf Se | Aqueous dispersions for antioxidants |
| EP1394186B1 (en) * | 2002-08-19 | 2013-06-26 | Shin-Etsu Chemical Co., Ltd. | Initiator blends for producing a vinyl chloride-based polymer by suspension polymerization |
| PT1698642E (en) | 2003-12-26 | 2009-01-13 | Shinetsu Chemical Co | Process for producing vinyl chloride polymer |
| EP2321367B1 (en) * | 2008-08-21 | 2014-06-11 | Masonite Corporation | Laser etching of polyvinylchloride |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578207A (en) * | 1980-06-17 | 1982-01-16 | Tokuyama Sekisui Kogyo Kk | Suspension polymerization of vinyl chloride |
| JPS60149608A (en) * | 1984-01-13 | 1985-08-07 | Mitsui Toatsu Chem Inc | Polymerization of vinyl chloride |
| US4659791A (en) * | 1984-09-11 | 1987-04-21 | The B.F. Goodrich Company | Internally coated reaction vessel for use in olefinic polymerization |
-
1987
- 1987-03-06 JP JP62051641A patent/JPH0788401B2/en not_active Expired - Lifetime
-
1988
- 1988-03-03 PT PT86893A patent/PT86893B/en active IP Right Grant
- 1988-03-04 EP EP88200407A patent/EP0281210B1/en not_active Expired - Lifetime
- 1988-03-04 MX MX010658A patent/MX167103B/en unknown
- 1988-03-04 NO NO880961A patent/NO168830C/en unknown
-
1989
- 1989-05-08 US US07/348,511 patent/US5011897A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0281210A3 (en) | 1990-08-22 |
| MX167103B (en) | 1993-03-04 |
| JPS63218711A (en) | 1988-09-12 |
| EP0281210B1 (en) | 1997-04-23 |
| JPH0788401B2 (en) | 1995-09-27 |
| NO168830B (en) | 1991-12-30 |
| NO880961L (en) | 1988-09-07 |
| NO880961D0 (en) | 1988-03-04 |
| NO168830C (en) | 1992-04-08 |
| US5011897A (en) | 1991-04-30 |
| EP0281210A2 (en) | 1988-09-07 |
| PT86893A (en) | 1988-04-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FG3A | Patent granted, date of granting |
Effective date: 19911108 |